properties of hard coating

7/29/2019 Properties of Hard Coating

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UNIVERSITY OF LJUBLJANA

FACULTY OF MATHEMATICS AND PHYSICS

Properties of PVD hard coatings

Author: Sreko PaskvaleMentor: dr. Peter Panjan

AbstractLast 2 to 3 decades application of PVD (physical vapour deposition) hard coatings exponentially

grows. However, the use of hard, thin films in the field of machine elements is the exceptionrather than the rule. The main problem lies in the relatively high contact pressure and the very

complex loading of machine components, which demand a hard resistance surface and a tough

core. In seminar it is represented major properties of PVD hard coatings, their growth defectsand reasons for them.

March 07


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Contents

1 Introduction 3

2 Mechanical properties of hard coatings 5

2.1 Hardness 5

2.1.1 How to achieve high hardness? 6

2.2 Adhesion 9

2.2.1 Energetics of Adhesion 10

2.3 Youngs modulus 10

2.4 Fracture strength 11

2.5 Residual stresses 12

3 Conclusion 17

References 18


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1 Introduction

For two decades, since they first appeared PVD hard coatings, they became unavoidable for wear

protection of tools for conventional machining (cutting tools, cold forming tools, plastic injection

moulding, tools for powder compaction).With PVD coated tools, we can:

increase productivity (longer tool life, higher cycle frequencies, less workpiece finishing)

reduce manufacturing costs

improve the quality of products (due to smoother surfaces, better dimensional stability,higher degrees of metal deformation and fewer manufacturing steps)

reduced lubricant consumption

All these advantages can be reach in metal cutting, sheet metal work, cold forming, pressure die-casting and plastic processing.

The application of PVD hard coatings to improve tribological properties of tools (e.g. for metal

cutting and forming) and machine elements (e.g. sliding bearings, valves) is constantlyincreasing. During the last decade the number of new coating materials, structures, combinations

and applications has increased exponentially. We could not imagine high speed machining, hard

machining and dry machining without appropriate hard protective coatings.

In the field of hard coatings great progress has been achieved in the previous years. Single-layer

coatings of transition metal nitrides and carbides (e.g. TiN) and multicomponent hard coatings(e.g. TiAlN) have been replaced in some cases with nanostructured (superlattice, nanocomposite,

nanogradient) and other superhard coatings (e.g. diamond, c-BN, CNx).Various multilayer

coatings have been also introduced in industrial production. They consist of a periodic structure

of two different materials. The thicknesses of individual layers are in the range of a fewnanometers up to few hundred nanometers.1

Hard coatings are made of hard material based on nitrides, carbides and borides of transitionmetals (such as TiN, CrN, (TiAl)N), carbon based coatings (diamond and diamond-like carbon

(DLC), alumina and cubic boron nitride (c-BN). The selection of appropriate protective coating

depends on specific tribological system (workpiece material, machining parameters and tool

materials). Basically two processes are used for hard coatings deposition: chemical vapourdeposition (CVD) and physical vapour deposition (PVD). PVD hard coatings can be prepared

either by evaporation or by sputtering of pure metal materials (e.g. Ti) in atmosphere of reactive

gas (N2, C2H2).2

Today, three types of coating structures are frequently found; single layer coatings, sandwich

coatings and gradient coatings (Fig. 1.1).


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Fig.1.1: Possible structures of tribological coatings

The primary hard coating requirements are:

good adhesion to tool substrate high microhardness at working temperature

high toughness

chemical inertness relative to the workpiece

The secondary requirements are:

fine-grain, crystallinemicrostructure

compressive residual stress crack-free and smooth surface

morphology

low heat transfer coefficient


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2 Mechanical properties of hard coatings

Properties of thin coatings can be arranged into tree different sets:

a. Structural and micro structural properties (thickness, crystal structure, chemicalcomposition, micro structure and texture, surface topography, roughness).

b. Physical and chemical properties (density, electrical properties, magnetic properties,thermal properties, optical properties, corrosion and oxidation resistance).

c. Mechanical properties (hardness, adhesion, mechanical stresses, fracture strength,wear, friction).

However, from tribological view, properties of hard coatings are thickness, Youngs modulus,microstructure, roughness, corrosion resistance, hardness, adhesion, fracture strength and internal

stresses.3

2.1 Hardness

Hardness is the resistance of a material to permanent penetration by another harder material

[ISO-14577-1]. It cannot be stressed enough that, for tribological applications, the substratehardness is of prime importance. If the thin fragile coating is not sufficiently supported, it will fail

at relatively low contact stresses because it cannot follow deformation of the substrate (so-called

'eggshell' effect). Hardness measurements are often used by coating developers to assess coatingquality, and to predict coating performance in various tribological applications. However, the

importance of a high, intrinsic coating hardness should not be exaggerated. Chemical stability,

fatigue resistance, or other properties, usually have higher influence on the wear resistance thanthe hardness. Apart from tooling applications, there are few tribosystems that demand coatingcomposite harnesses above 2000 HV. In general, oxides and nitrides used as coating materialshave hardness values of 1500-3000 HV, whereas for carbides and borides these values range

between 2000-3600 HV.4

An increased hardness is associated with a reduced ductility for virtually all types of materials.Thus, hardness and ductility should both be considered when discussing wear properties. The

hardness of modern PVD and CVD coatings used in tools and machine elements is usually

sufficient, i.e., the hardness exceeds that of almost all wearing particles and thus, wear

mechanisms other than abrasion dominate. Therefore, tribological coating development today

should be directed more towards improved ductility, e.g., by introducing multiple layers or layerswith gradients in hardness and ductility, and towards improved chemical and thermal stability.

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It is also important to recognize the fact that hardness is not a material constant. Any measured

hardness value will depend on coating thickness, substrate hardness, geometry of the indenter,

and several other test parameters. Therefore, special experimental techniques must generally beutilized. Intrinsic hardness values of thin hard coatings cannot be determined directly by

conventional micro-hardness testing, as they usually are strongly influenced by the substrate.


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Several approaches are used; one is to measure the hardness of the coated component at several

loads and extrapolate towards infinitely low loads. A rule of thumb in Vickers hardness testing is

that the coating thickness should be more than ten times the indentation depth, for substrateinfluence to be negligible; other approaches involve the application of physical models, e.g., the

Jonsson/Hogmark model. The use of very low load techniques, nano-indentation, is in progress.

Nano-indentation produces a much richer set of information about the mechanical properties ofthin films than just a simple hardness number, provided that the indentation depth versus load

curve is interpreted correctly. 5

Representative PVD coating hardness values are given in Fig. 2.1.1

Fig. 2.1.1: Intrinsic hardness of commercially available

PVD coatings deposited on both high-speed steeland cold work steel substrates 6

2.1.1 How to achieve high hardness?

1. Use intrinsic hard materials

binary nitrides, carbides, borides (


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bonding. Diamond is the hardest material known and has purely covalent bonds, while c-BN,

the second hardest material, have also a small ionic contribution.

2. Alloy them with additional elements

Example: ternary nitrides, carbonitrides ( poor adhesion) and no residual stress(==> no crack retardation)

4. Superlattice coatings

Multilayer coatings of materials with similar crystal structures, while the thickness of the

individual layers is in nm-scale (also known as superlattice). Superlattice strengthening is

well known from classical metallurgy (Fig. 2.1.2 and 2.1.3)

Fig. 2.1.2:Different types of multilayer coatings: (a )small number of single layers,(b) high number

of nonisostructural single layers, (c,d) high number of isostructural single layers-superlattice7


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Fig 2.1.3:Achieving high hardness by superlattice coatings 7

5. Decrease grain size

d > 20 nm: hardeningHall-Petch relation (2.1.1) d 10 nm: no dislocations can propagate

deformation mainly by grain boundary sliding

substantial increase in hardness

d < 5 nm: softening (larger fraction of material in grain boundaries)

d 0: amorphous

Fig. 2.1.4: With grain size decreased no dislocations can propagate, deformation mainly bygrain boundary sliding, substantial increase in hardness7


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The hardness as well as the yield strength and toughness of PVD hard coatings are also

influenced by the grain size within them; as the grain size is reduced the coating yield strength

and hardness increase, as expected from a simple Hall-Petch (2.1.1). This phenomenon is validthin coatings down to nm-sized grains. Small grain sizes cause a hardening of the material in

agreement with the Hall-Petch relation:3

2.1.1

where H0 is intrinsic hardness of monocrystal, d is average size of crystal grains and k is the

constant of material.

2.2 Adhesion

The term adhesion refers to the interaction between the closely contiguous surfaces of adjacentbodies, i.e., a film and substrate. Adhesion is defined as the condition in which two surfaces are

held together by valence forces or by mechanical anchoring or by both together (Fig. 2.2.1).

Fig. 2.2.1: Four types of adhesion; (1)smoothtransition, (2)compound layer, (3)diffusion bond,

(4)mechanical locking8

Adhesion to the substrate is certainly the first attribute a film must possess before any of its otherproperties can be further successfully exploited. Even though it is of critical importance adhesion

is one of the least understood properties. The lack of a broadly applicable method forquantitatively measuring "adhesion" makes it virtually impossible to test any of the proposed

theories for it. This state of affairs has persisted for years and has essentially spawned two

attitudes with respect to the subject. The "academic" approach is concerned with the nature of


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bonding and the microscopic details of the electronic and chemical interactions at the film-

substrate interface. Clearly, a detailed understanding of this interface is essential to better predict

the behavior of the macrosystem, but atomistic models of the former have thus far been unsuccess-fully extrapolated to describe the continuum behavior of the latter. For this reason the

"pragmatic" approach to adhesion by the thin-film technologist has naturally evolved. The

primary focus here is to view the effect of adhesion on film quality, durability, andenvironmental stability. Whereas the atomic binding energy may be taken as a significantmeasure of adhesion for the academic, the pragmatist favors the use of large-area mechanical

tests to measure the force or energy required to separate the film from the substrate. Both

approaches are valuable in dealing with this difficult subject.

2.2.1 Energetics of Adhesion

From a thermodynamic standpoint the work WA required to separate a unit area of two phases

forming an interface is expressed by9

WA = f+ s+ fs. 2.2.1

The quantities f and s are the specific surface energies of film and substrate, and fs is theinterfacial energy. A positive WA denotes attraction (adhesion) and a negative WA implies

repulsion (de-adhesion). The workWAis largest when materials of high surface energy come into

contact such as metals with high melting points. Conversely, WAis smallest when low-surface-energy materials such as polymers are brought into contact. When fands are identical, then an

interfacial grain boundary forms where f + s >fs.Under these circumstances, f = sand fs isrelatively small; e.g., fs1/3 s in metals. If, however, a homoepitaxial film is involved, thenfs=0 by definition, and WA = 2s . Attempts to separate an epitaxial film from its substrate willlikely cause a cohesion failure through the bulk rather than an adhesion failure at the interface.

When the film-substrate combination is composed of different materials, fs may be appreciable,thus reducing the magnitude ofWA , Interfacial adhesion failures tend to be more common undersuch circumstances. In general, the magnitude of WA increases in the order (a) immiscible

materials with different types of bonding, e.g., metal-polymer, (b) solid-solution formers, and (c)

same materials. Measured values of adhesion will differ from intrinsic WA values because of

contributions from chemical interactions, interdiffusional effects, internal film stresses,interfacial impurities, imperfect contact, etc.

Sufficient adhesion is generally achieved by appropriate surface pre-treatment, cleaning and, inmany cases, by using adhesion promoting interlayer (e.g. Aluminum is used as interlayer for

TiAlN deposited coatings). Machining operations may change the structure of steel surfaces

thereby creating coating adhesion problems. Substrates with increased roughness offer betteradhesion. Adhesion of tribological coatings is routinely tested using the scratch test.9

2.3 Youngs modulus

Youngs modulus, also known as the modulus of elasticity (E), is difficult to determine due to the

low thickness of the coatings. On the other hand, its value has a strong influence on the contact


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stress field, coating delamination and detachment, coating fracture, residual stress state within the

coating, etc.

Usually, thin hard coatings have a Young's modulus higher than the substrate, and also often a

lower coefficient of thermal expansion. As a result, an increase of the surface temperature may

thus cause the introduction of tensile stresses in the coating. According to the literature data, theE of a TiN coating can vary in the range from 270 to 600 GPa.7

2.4 Fracture strength

Coating wear and removal often involve crack initiation and propagation processes. Hard

coatings, particularly those produced by PVD techniques, are usually brittle, i.e., their tensile

strength is low compared with their yield stress in compression. This is a result of their structure,

with columnar grains often extending through the whole coating thickness. Fracture strength is acritical parameter in situations where the coating has to deform to accommodate substrate

deformation. Therefore, in the tribological contacts operating at high contact pressure, mechanicalimpact or rapid heating, the fracture strength can be more important than the coating hardness.

The possible mechanisms of coating failure are illustrated in Fig. 2.4.1. In the case of a

monolayer coating (Fig. 2.4.1(a)), microcrack initiation occurs simultaneously at the coating

surface and the coating-substrate interface. Thus, coating fracture develops through the entirecross-section as a result of the propagation and coalescence of local microcracks. On the other

hand, for multilayer coatings, microcracks develop mainly in the vicinity of the top surface and,

in turn, the interfaces between layers can substantially change the direction of the initial crack when

it penetrates deep into the coating. This means that multilayer coatings fail in a laminar manner. Inconsequence, multilayer as well as multiple structures can enhance the resistance of coatings

against crack propagation.

Fig. 2.4.1: Schematic representation of mechanical destruction of singlelayer (a) and multilayer coatings (b). Ischematic coating structure; II,IIIsuccessive stages of failure.

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Fig. 2.4.2: Crack propagation for monolayer and multilayer coatingswhen milling11

In the milling process, which is a typical interrupted cutting, the absorption of cracks is the mostimportant requirement for intrinsic coating properties. In fact, monolayer coatings, such as TiN or

TiAlN, lead the crack rapidly to the substrate (Fig. 2.4.2(a)). It is clear from Fig. 2.4.2(b) that the

superiority of the TiCN coating in milling can only be achieved by the multilayer structure

Fig. 2.4.3: hard coatings crack spreading: (a) classic coating, (b) coating with hightensile stresses, (c) coating with fine-grained microstructure, (d) multi layer coating

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2.5 Residual stresses

Almost any type of thin hard coating contains residual stressesresulting from the manufacturing-process. They can be a result of growth mechanisms, or rapid cooling from a high depositiontemperature if there is a substantial difference in thermal expansion between the coating and

substrate materials. Typically, CVD coatings on cemented carbide substrate exhibit tensile or

compressive stresses depending on the material combination, and PVD coatings deposited onhighspeed steel display compressive stresses. The general stress distribution for these two cases

is shown in Fig. 2.5.1.


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Fig. 2.5.1: General stress distribution in the coated tools: (a) CVD coating of

5-10 m; (b) PVD coating of 2-6 m7

Coating residual stresses may improve the performance of coated components in several ways;

some of them have already been discussed. On the other hand, compressive stresses in coatingsmay be desirable because they increase hardness and resistance to fatigue wear. The internal stress

(also residual stress) combines the intrinsic stress, resulting from the growth process, and thethermal stress, arising from a mismatch in thermal expansion coefficient between the coating and

the substrate.

Implicit is that the stresses and the effects they produce are the result of externally appliedforces. After the load is removed, the stresses are expected to vanish. On the other hand, thinfilms are stressed even without the application of external loading and are said to possessinternal or residual stresses. The origin and nature of these internal residual stresses are thesources of many mechanical effects in films. Residual stresses are, of course, not restricted tocomposite film-substrate structures, but occur universally in all classes of homogeneousmaterials under special circumstances.

A state of nonuniform plastic deformation is required, and this frequently occurs duringmechanical or thermal processing. For example, when a metal strip is reduced slightly by rollingbetween cylindrical rolls, the surface fibers are extended more than the interior bulk. The latterrestrains the fiber extension and places the surface in compression while the interior is stressedin tension. This residual stress distribution, is locked into the metal, but can be released like ajack-in-the-box. Machining a thin surface layer from the rolled metal will upset the mechanicalequilibrium and cause the remaining material to bow. Residual stresses arise in casting, welds,machined and ground materials, and heat-treated glass. The presence of residual stresses isusually undesirable, but there are cases where they are beneficial. Tempered glass and shot-

peened metal surfaces rely on residual compressive stresses to counteract harmful tensilestresses applied in service.

A model for the generation of internal stress during the deposition of films is illustrated in Fig.2.5.2


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Fig.2.5.2: Sequence of events leading to (a) residual tensilestress in film, (b) residual compressive stress in film 9

The formulas that have been used in virtually all experimental determinations of film stress are

variants of an equation first given by Stoney in 1909. This equation can be derived with

reference to Fig. 2.5.3, which shows a composite film-substrate combination of width w.

Fig. 2.5.3: Stress analysis of film-substrate combination: (a)

composite structure; (b) free-body diagrams of film and substrate withindicated interfacial forces and end moments; (c) elastic bending of

beam under applied end moment11


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The film thickness and Youngs modulus are df and Ef, respectively, and the correspondingsubstrate values are ds and Es. Due to lattice misfit, differential thermal expansion, film growth

effect, etc., mismatch forces arise at the film-substrate interface. After some calculation we getequation known as Stoney formula: 9

f= 2.5.1

Equation 2.5.1 is a good approximation to f only ifds is much larger than df. Values off are

determined through measurement ofR.

Residual stresses in homogeneous coatings do not generate any normal or shear stresses at the

interface if the substrate is perfectly flat and smooth, and of infinite extent, as illustrated in Fig.

2.5.7 a. However, engineering components generally deviates from this case. The fourelementary cases shown in Fig. 2.5.4 be, or combinations of them, represent commondeviations such as edges, pores, scratches, and ridges. Interfacial stresses induced for

compressive *

are indicated in the figures. This residual stress level *= x= y is characteristic

for a specific material combination and manufacturing process.

Fig. 2.5.4: (a) Illustration of an infinite coating on a perfectly flat and smooth substrate having a

compressive characteristics residual stress *. (b)(d) Tensile and shear stresses induced at an

edge, at the edges of a pore, in a grove, and at a ridge, respectively. 11

Only to mention, in the present investigation, the local stress distribution at corners, edges and

rough interfaces in residually stressed coating systems are studied by finite element calculations(FEM) Fig.2.5.5. Numerical results are presented for a number of coating substrate

combinations representative for tribological components such as forming and cutting tools andmachine elements. Elucidative examples of cohesive and interfacial failure are demonstrated

experimentally for some selected coating systems.


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Fig. 2.5.5:Models and definitions for stress calculations. (a) Coating on smooth 90 substrateedge. (b) An edge of a terminated coating. (c) A periodic rough substrate surface. 11


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3 Conclusion

From the above it should be clear that a coating is far from a panacea. Both coating and substrate

properties must be carefully considered to obtain a good composite material. The measurement of

thin coating properties often requires special skills, but many of the techniques are becoming wellestablished. The successful implementation of coatings to address tribological problems relies on the

consideration of all of these different aspects in the design of the coated component, using asystematic approach.

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Surface engineering is one of the most important technologies that may contribute to a sustainabledevelopment in the industrial world, through the conservation of earth resources, a reduction of

waste, and energy savings. 8

The introduction of PVD coatings in industry is growing each year but still faces problems such

as the lack of knowledge - very often on the materials side of the tribological system and also

problems related to the coating itself (e.g. adhesion, reproducibility, coating of complexgeometries.

The most successful introduction has taken place for metal cutting applications where TiN,Ti(C,N), (Ti,Al)N, CrN, superlattice and nanocomposite coatings as well as CVD diamond

coatings. The market share of other tools is also growing. Other types of PVD coatings like

DLC, WC/C, MoS2 are also used in industrial practice for protection of mechanical components.

Global industry trends towards HSM, dry machining, dry forming, minimal use of lubricants,

elimination of toxic by-products in manufacturing are all supported by PVD technologyimplementation.


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References

1S. Hogmark et al., Surface and Coatings Technology, 90 (1997), 247-257

2W.D. Sproul, Surface and Coatings Technology, 131 (2000), 433-440

3 P. Panjan, M. ekada,Zaita orodij s trdimi PVD prevlekami, Ljubljana 2005, 79-1114

J.A Thornton,J. Vac. Science Techology, 11 (1974), 666-7605

P.J. Burnett, D.S. Rickerby. Thin Solid Films 157 (1988), 2336

P. Hedenqvist et al., Surface and Coatings Technology, 97 (1997), 212-2177

W.Grzesik,Advanced Protective Coatings for Manufacturing and Engineering,

Cincinnati 2003, 40-558

J. Meneve at al., Surface and Coatings Technology, 94-95 (1997), 476-4829

M.Ohring, The Material Sci. of Thin Films, San Diego 1992, 416-41810

B. Buchmeister,Izdelovalni postopki-preoblikovanje, Maribor 2002, 9-3411

U.Wiklund et al., Wear, 232 (1999), 262-26912

S. Hogmark et al., Wear, 246 (2000), 20-33

properties of hard coating

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